EP4358103B1 - Aimant en néodyme-fer-bore fritté haute performance et son procédé de préparation - Google Patents

Aimant en néodyme-fer-bore fritté haute performance et son procédé de préparation

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Publication number
EP4358103B1
EP4358103B1 EP22845354.4A EP22845354A EP4358103B1 EP 4358103 B1 EP4358103 B1 EP 4358103B1 EP 22845354 A EP22845354 A EP 22845354A EP 4358103 B1 EP4358103 B1 EP 4358103B1
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Prior art keywords
alloy
diffusion
temperature
iron
preparation
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EP4358103C0 (fr
EP4358103A4 (fr
EP4358103A1 (fr
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Zhiqiang Li
Ting Zhang
Nan Zhao
Lingwen XUE
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Nantong Zhenghai Magnet Co Ltd
Yantai Zhenghai Magnetic Material Co Ltd
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Nantong Zhenghai Magnet Co Ltd
Yantai Zhenghai Magnetic Material Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/08—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/08—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/086—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together sintered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0293—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F7/00—Magnets
    • H01F7/02—Permanent magnets [PM]
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic

Definitions

  • the present disclosure belongs to the field of rare-earth permanent magnet materials, and particularly relates to a high-performance sintered neodymium-iron-boron magnet and a preparation method therefor.
  • neodymium-iron-boron magnets differ in their performance, with the high-performance sintered neodymium-iron-boron magnet being the most superior in terms of performance.
  • the high-performance sintered neodymium-iron-boron magnet is a sintered neodymium-iron-boron permanent magnet material with the sum of Hcj (intrinsic coercivity, KOe) and (BH)max (maximum magnetic energy product, MGOe) of greater than 60, which is prepared by the procedures of rapid hardening and strip casting, hydrogen decrepitation, jet milling, pressing, sintering, and the like, and by adopting an oxygen-free process and the like.
  • the patent application with the publication number CN101707107A discloses a method for manufacturing a rare-earth permanent magnet material with high remanence and high coercivity, which comprises the process steps of preparing a master alloy, crushing, molding, sintering to prepare a sintered magnet, aging treatment, mechanical processing, and surface treatment, and is characterized in that after the process step of sintering to prepare the sintered magnet R1-T-B-M1, the sintered magnet is embedded in a pre-mixed powder consisting of a heavy rare-earth HR2M2 alloy powder and one or more of powdered R3 oxides, R4 fluorides, and R5 fluorides; wherein HR2 is at least one of Dy, Ho, and Tb; M2 is at least one of Al, Cu, Co, Ni, Mn, Ga, In, Sn, Pb, Bi, Zn, and Ag; R3, R4, and R5 are one or more of rare-earth elements including Y and Sc.
  • magnets need to be arranged at intervals by operators, which reduces the operational efficiency; moreover the production efficiency is also reduced due to the fact that the arrangement at intervals affects the loading capacity.
  • the patent application with the publication number CN106298219A discloses a method for preparing an R-T-B rare-earth permanent magnet, comprising the following steps: a) preparing an R L u R H v Fe 100-u-v-w-z B w M z rare-earth alloy for use as a diffusion source, wherein the R L represents at least one of the elements Pr and Nd; R H represents at least one of the elements Dy, Tb, and Ho; M represents at least one of the elements Co, Nb, Cu, Al, Ga, Zr, and Ti; the rare-earth alloy contains a main phase structure of an R-Fe-B tetragonal crystal; u, v, w, and z are weight percentages of substances, and u, v, w, and z satisfy the following relationships: 0 ⁇ u ⁇ 10, 35 ⁇ v ⁇ 70, 0.5 ⁇ w ⁇ 5, and 0 ⁇ z ⁇ 5; b) crushing the R L u
  • an R-Fe-B alloy is adopted as the diffusion source alloy.
  • the R-Fe-B alloy is used as the diffusion source and the B content of the diffusion source is too high, the melting point of the diffusion source may become relatively high, resulting in a low diffusion rate. That is, the amount of active ingredient that gets into the substrate within the same period of time is small, and once the temperature of diffusion is increased, the main phase grains will be destroyed, thereby weakening the diffusion effect. Therefore, the diffusion efficiency is poor and the desired performance is not achieved.
  • the patent application with the publication number CN107731437A discloses a method for reducing irreversible losses of a sintered neodymium-iron-boron sheet magnet, wherein the light rare-earth metal Nd or Pr, or a PrNd alloy rapid-hardening sheet, is mixed with a low-quality sintered neodymium-iron-boron sheet magnet at a certain ratio, and then the mixture is put into a diffusion furnace and subjected to a heat treatment at a certain rotational speed and a certain temperature; finally, the magnet obtained after the diffusion is annealed at 460 °C-520 °C for 3-5 h.
  • the light rare-earth metal Nd or Pr, or a PrNd alloy rapid-hardening sheet is adopted as the diffusion source, and the element Nd or Pr is diffused into the surface layer region of the sintered neodymium-iron-boron sheet magnet block to repair damaged microstructures in the surface region of the sintered neodymium-iron-boron sheet magnet, thereby improving the coercivity of the sintered neodymium-iron-boron sheet magnet.
  • the diffusion source adopted in the process is light rare-earth elements, which have limited diffusion effect, the process is only relatively effective for sheet products, the improvement in its Hcj performance is limited (an increase of only 1-3 KOe), and the Hcj performance-improving effect is not significant for slightly thicker products.
  • the patent application with the publication No. CN105321702A discloses a method for improving the coercivity of a sintered NdFeB magnet, wherein the coercivity of the sintered NdFeB magnet is improved by a grain boundary diffusion method using a grain boundary diffusion alloy material free of heavy rare-earth elements; the diffusion alloy consists of Re 100-x-y Al x M y , wherein Re is one or more of Ce, Pr, and Nd; M is one or more of Mg and Cu; 2 ⁇ X ⁇ 33; 0 ⁇ y ⁇ 5.
  • the process comprises the following specific steps: performing smelting under vacuum to obtain the diffusion alloy, making the diffusion alloy into a powder or rapidly quenching the diffusion alloy into a thin strip, coating the surface of a sintered neodymium-iron-boron magnet with the diffusion alloy, then performing diffusion in a vacuum furnace at 600-1000 °C for 1-10 hours, and performing tempering at 500 °C for 1-5 hours.
  • this method also suffers from the following drawbacks: as the diffusion process involves coating the surface of the magnet with the diffusion source, the diffusion source powder or debris can easily stick to the surface of the magnet; moreover, the magnet may have varying degrees of pit defects on the lower surface due to gravity, which affect the size and/or appearance of the product.
  • the patent application with the publication No. CN103003899A discloses a treating apparatus comprising a diffusion processing part, a separation part, and a heat treatment part, wherein the diffusion processing part is used for heating a Re-Fe-B-based sintered magnet and a diffusion source of a metal or an alloy of a metal RH containing a heavy rare-earth element while rotating; the separation part selectively separates the RH diffusion source from the sintered magnet and the RH diffusion source received by the diffusion processing part; the heat treatment part is used for performing a heat treatment on the Re-Fe-B sintered magnet with the diffused heavy rare-earth element after the RH diffusion source is removed.
  • Temperature lows are easily generated at the linking parts of different chambers in the apparatus, and it is difficult to maintain a uniform temperature zone in the furnace; in addition, since the treatments in the diffusion area and the heat treatment area take more time while the treatment in the separation part takes less time, this continuous treatment furnace cannot better improve efficiency, for example, when the diffusion area has materials and the separation part and the heat treatment part have no material are waiting for materials. Thus, the arrangement of the separate diffusion part, the separate separation part, and the separate heat treatment part does not give the apparatus a significant advantage.
  • CN111636035A discloses a sintered neodymium-iron-boron magnet and a preparation method therefor.
  • M 1 is preferably any two of the elements Ti, Zr, and Al, and the mass ratio of the two elements is 1:1 to 2:1, illustratively 1:1, 1.5:1, 1:2, or 2:1.
  • R H is Dy
  • M 1 is two of Ti and Al
  • x 85%
  • z 0.4%
  • y 14.6%
  • the R H x M 1 y B z alloy is Dy 85% Ti 9.73% Al 4.87% B 0.4% .
  • the R H x M 1 y B z alloy is Tb 80% Ti 11.82% Zr 7.88% B 0.3% .
  • the R H x M 1 y B z alloy may be in the form of a sheet, for example, with an average thickness of ⁇ 10 mm, preferably ⁇ 5 mm, and illustratively 1 mm, 1.8 mm, 2 mm, 3 mm, 4 mm, or 5 mm.
  • the present disclosure further provides a preparation method for the R H x M 1 y B z alloy described above, wherein the preparation method comprises: subjecting starting materials comprising the element R H , the element M 1 , and the element B to smelting and rapid hardening to prepare the R H x M 1 y B z alloy.
  • the element R H , the element M 1 , and the element B are as defined above.
  • the smelting is performed in an inert atmosphere; for example, the inert atmosphere may be provided by argon and/or helium, preferably by argon.
  • the smelting is performed at a temperature of 1350 °C to 1550 °C, illustratively 1350 °C, 1450 °C, 1480 °C, or 1500 °C; further, the smelting is performed with a temperature holding time of 0-30 min, illustratively 5 min, 10 min, 20 min, or 30 min.
  • the smelting is performed until the starting materials are melted down into an alloy liquid.
  • the preparation method further comprises cooling the alloy liquid obtained by the smelting to a casting temperature.
  • the cooling is performed at a rate of 3-9 °C/min, illustratively 3 °C/min, 4 °C/min, 6 °C/min, 8 °C/min, or 9 °C/min.
  • the casting temperature is 1330 to 1530 °C, illustratively 1340 °C, 1400 °C, 1430 °C, or 1450 °C.
  • the preparation method comprises: performing strip casting of the alloy liquid that has been cooled to the casting temperature to obtain an R H x M 1 y B z rapid-hardening alloy sheet.
  • the average thickness of the R H x M 1 y B z rapid-hardening alloy sheet is ⁇ 10 mm, preferably ⁇ 5 mm, and illustratively 1 mm, 2 mm, 3 mm, 4 mm, or 5 mm.
  • the preparation method comprises: completely smelting starting materials containing the element R H , the element M 1 , and the element B into an alloy liquid in an inert atmosphere, cooling the alloy liquid to a casting temperature, and performing strip casting to obtain an P H x M 1 y B z rapid-hardening alloy sheet with an average thickness of ⁇ 10 mm.
  • the present disclosure further provides use of the R H x M 1 y B z alloy described above in the preparation of a sintered neodymium-iron-boron material, preferably a high-performance sintered neodymium-iron-boron material.
  • the high-performance sintered neodymium-iron-boron material means a sintered neodymium-iron-boron permanent magnet material with the sum of Hcj (intrinsic coercivity, KOe) and (BH)max (maximum magnetic energy product, MGOe) of greater than 60.
  • the R H x M 1 y B z alloy described above is used as a diffusion source in the preparation of a sintered neodymium-iron-boron material.
  • the present disclosure further provides a method for preparing a sintered neodymium-iron-boron magnet, comprising a diffusion heat treatment using R 1 m Fe n B p M 2 w as a substrate and an R H x M 1 y B z alloy as a diffusion source, wherein the R H x M 1 y B z alloy is as defined above and wherein, in the R 1 m Fe n B p M 2 w substrate, the R 1 is selected from one, two or more of the elements Pr, Nd, Dy, Tb, Ho, Gd, Ce, La, and Y; Fe represents the element iron; B represents the element boron; M 2 is selected from one, two or more of the elements Ti, Zr, Co, V, Nb, Ni, Cu, Zr, Al, and Ga; m represents the weight percentage content of R 1 , and 35% ⁇ m ⁇ 27%; n represents the weight percentage content of Fe, and 70% ⁇ n ⁇ 60%; p represents the weight percentage content
  • the R 1 is selected from Nd and Dy
  • the M 2 is selected from Ti, Cu, Ga, and Co.
  • m 29%, 29.5%, 30%, 31%, or 32%.
  • n 62%, 64%, 66.5%, 67.5%, or 68.5%.
  • p 0.8%, 1.0%, or 1.1%.
  • a preparation method for the R 1 m Fe n B p M 2 w substrate comprises smelting, milling, pressing, sintering, and aging to prepare a magnet, and may further comprise the steps of mechanical processing and surface treatment.
  • the thickness of the substrate in an orientation direction is no more than 30 mm, e.g., 1-30 mm, and may be divided into 1-8 mm, 8-15 mm, 15-20 mm, or 20-30 mm.
  • the Hcj (intrinsic coercivity) of the sintered neodymium-iron-boron magnet is no less than 20 kOe; preferably, the Hcj is 21 to 29 kOe, illustratively 23.61 kOe, 24.45 kOe, 25.63 kOe, 26.40 kOe, 27.50 kOe, or 28.89 kOe.
  • the Br of the sintered neodymium-iron-boron magnet is 13.8 to 14.6 kGs, illustratively, 13.85 kGs, 13.94 kGs, 14.1 kGs, 14.2 kGs, 14.3 kGs, or 14.55 kGs.
  • the density of the sintered neodymium-iron-boron magnet is 7.50 to 7.60 g/cm 3 , illustratively, 7.50 g/cm 3 , 7.56 g/cm 3 , or 7.60 g/cm 3 , and preferably 7.56 g/cm 3 .
  • a method is comprising the following steps: uniformly mixing the diffusion source R H x M 1 y B z alloy and the substrate R 1 m Fe n B p M 2 w and performing a diffusion heat treatment to obtain the sintered neodymium-iron-boron magnet.
  • the mass ratio of the diffusion source R H x M 1 y B z alloy to the substrate R 1 m Fe n B p M 2 w is (1 to 5):1, illustratively 1:1, 1.5:1, 2:1, 2.3:1, 3:1, or 5:1.
  • the diffusion heat treatment is performed using a staged heating and cooling mode.
  • a three-staged heating and cooling mode is used.
  • the temperature in the first stage of the three-staged heating and cooling mode, is raised to 300 to 650 °C, illustratively 400 °C, 480 °C, 550 °C, or 650 °C, and held for 1-8 h, illustratively 2 h, 4 h, 6 h, or 8 h;
  • the rate of heating is 3 to 15 °C/min, illustratively 6 °C/min or 10 °C/min, and the rate of cooling is 5 to 30 °C/min, illustratively 6 °C/min, 10 °C/min, or 20 °C/min.
  • the diffusion heat treatment further comprises an aging treatment.
  • the aging treatment is performed at a temperature of 400 to 680 °C, illustratively 400 °C, 500 °C, 520 °C, 600 °C, or 680 °C; and the aging treatment is performed with a temperature holding time of 2 to 10 h, illustratively 2 h, 4 h, 6 h, 8 h, or 10 h.
  • Comparative Example 1 differs from Example 1 in that the R H x M 1 y B z diffusion source consists of the following elements: 85% Tb, no B, and the balance of Ti + Al (mass ratio of 2:1).
  • Example 1 Comparison of the appearances and magnetic properties of the magnets obtained in Example 1 and Comparative Examples 1 and 2 Item Ratios of elements in diffusion material (mass ratios) Thickness of substrate product Diffusion process Appearance and magnetic properties after diffusion Appearance adhesion ratio Br (kGs) Hcj (kOe)
  • Example 1 85%Tb, 0.4%B, 9.73%Ti, 4.87%Al 5mm Three-staged 0.005% 14.20 26.1 Comparative Example 1 85%Tb, 0%B, 10%Ti, 5%Al 5mm Three-staged 2.01% 14.18 26.2 Comparative Example 2 85%Tb, 1%B, 9.33%Ti, 4.67%Al 5mm Three-staged 0.006% 14.26 25
  • the addition of a proper amount of B can improve the melting point of the R H x M 1 y B z alloy to some extent, so as to avoid adhesion caused by the molten surface of the R H x M 1 y B z diffusion source alloy, and reduce the appearance adhesion ratio between magnets, thereby improving the appearance of the magnets discharged from the furnace and effectively enhancing the Hcj of the magnets; however, if the B content is too high, the diffusion channel may be affected, and thus the improvements to the Hcj of the magnets after diffusion may be affected.
  • Comparative Example 3 differs from Example 2 only in that the R H x M 1 y B z diffusion source consists of the following elements: 70% Tb, 0.3% B, and the balance of Ti + Zr (mass ratio of 1.5:1).
  • Comparative Example 4 differs from Example 2 in that a two-staged treatment was adopted for the diffusion in step (7). That is, the temperature for the first stage of the diffusion was 400 °C, and the temperature was held for 4 h; the temperature for the second stage was 930 °C, and the temperature was held for 30 h; for both stages, the rate of heating was 6 °C/min, and the rate of cooling was 10 °C/min; aging was performed at 500 °C for 6 h.
  • Example 2 differs from Example 2 in that:
  • Example 2 The appearances and magnetic properties of the magnets obtained in Examples 2-3 and Comparative Examples 3-4 were tested, and the results are shown in Table 2 below. Table 2. Comparison of the appearances and magnetic properties of the magnets obtained in Examples 2-3 and Comparative Examples 3-4 Item Ratios of elements in diffusion material (mass ratios) Thickness of substrate product Diffusion process Performance after diffusion Br (kGs) Hcj (kOe)
  • Example 2 80%Tb, 0.3%B, 11.82%Ti, 7.88%Zr 10mm Three -staged 14.25 25.9 Comparative Example 3 70%Tb, 0.3%B, 17.82%Ti, 11.88%Zr 10mm Three -staged 14.30 25.2
  • Example 3 80%Tb, 0.3%B, 11.82%Ti, 7.88%Zr 15mm Three -staged 14.27 25.7 Comparative Example 4 80%Tb, 0.3%B, 11.82%Ti, 7.88%Zr 10mm Two -staged 14.29 25.0
  • Example 3 shows that when the thickness of the R 1 m Fe n B p M 2 w substrate is increased, the Hcj performance of the post-diffusion magnet can also be improved by adjusting the duration of the three-staged heating and cooling diffusion treatment.

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Claims (9)

  1. Alliage RH xM1 yBz, dans lequel le RH est choisi parmi un ou deux des éléments Dy et Tb ; M1 est choisi parmi un, deux ou trois des éléments Ti, Zr et Al ; le B représente l'élément bore ; x, y et z représentent les pourcentages pondéraux des éléments, et x, y et z satisfont les relations suivantes : 75 % ≤ x ≤ 90 % ; 0,1 % ≤ z ≤ 0,5 % et y = 1-x-z.
  2. Alliage RH xM1 yBz selon la revendication 1, dans lequel dans l'alliage RH xM1 yBz, 80 % ≤ x ≤ 85 % ; 0,15 % ≤ z ≤ 0,3 % et y = 1-x-z ;
    de préférence, dans l'alliage R1 xM1 yBz, M1 est deux éléments quelconques parmi Ti, Zr et Al, et le rapport massique des deux éléments est de 1:1 à 2:1 ;
    de préférence, l'alliage RH xM1 yBz peut se présenter sous forme d'une feuille, par exemple, avec une épaisseur moyenne ≤ 10 mm ; de préférence, l'épaisseur moyenne est ≤ 5 mm.
  3. Procédé de préparation de l'alliage R1 xM1 yBz selon la revendication 1 ou 2, dans lequel le procédé de préparation comprend : la soumission de matières de départs comprenant l'élément RH, l'élément M1 et l'élément B à une fusion et à un durcissement rapide pour préparer l'alliage RH xM1 yBz ;
    de préférence, l'élément RH, l'élément M1 et l'élément B sont tels que définis dans la revendication 1 ;
    de préférence, la quantité de l'élément RH, de l'élément M1 et de l'élément B est pesé selon un rapport pondéral de RH:M1:B = x:y:z, dans lequel x, y et z sont tels que définis dans la revendication 1.
  4. Procédé de préparation selon la revendication 3, dans lequel la fusion est réalisée sous atmosphère inerte ; de préférence, l'atmosphère inerte est fournie par de l'argon ;
    de préférence, la fusion est réalisée à une température de 1350 °C à 1550 °C, et la fusion est réalisée avec un temps de maintien de 0 à 30 min ;
    de préférence, la fusion est réalisée jusqu'à ce que les matières de départ soient fondues en un alliage liquide ;
    de préférence, le procédé de préparation comprend en outre le refroidissement de l'alliage liquide obtenu par la fusion à une température de coulée ;
    de préférence, le refroidissement est réalisé à une vitesse de 3 à 9 °C/min ;
    de préférence, la coulée est réalisée à une température de 1330 à 1530 °C.
  5. Procédé de préparation selon la revendication 3 ou 4, dans lequel le procédé de préparation comprend : la réalisation d'une coulée en bande de l'alliage liquide qui a été refroidi à la température de coulée afin d'obtenir une feuille d'alliage RH xM1 yBz à durcissement rapide ;
    de préférence, l'épaisseur moyenne de la feuille d'alliage RH xM1 yBz à durcissement rapide est ≤ 10 mm ; de préférence, l'épaisseur moyenne est ≤ 5 mm ;
    de préférence, le procédé de préparation comprend : la fusion complète des matières de départ contenant l'élément RH, l'élément M1 et l'élément B en un alliage liquide sous atmosphère inerte, le refroidissement de l'alliage liquide à la température de coulée, puis la réalisation d'une coulée en bande afin d'obtenir une feuille d'alliage RH xM1 yBz à durcissement rapide d'une épaisseur moyenne ≤ 10 mm.
  6. Utilisation de l'alliage RH xM1 yBz selon la revendication 1 ou 2 dans la préparation d'un matériau fritté néodyme-fer-bore, de préférence un matériau fritté néodyme-fer-bore à haute performance, dans laquelle
    de préférence, l'alliage RH xM1 yBz selon la revendication 1 ou 2 est utilisé comme source de diffusion dans la préparation du matériau fritté néodyme-fer-bore.
  7. Procédé de préparation d'un aimant fritté néodyme-fer-bore, comprenant un traitement thermique par diffusion utilisant R1 mFenBpM2 w comme substrat et un alliage RH xM1 yBz comme source de diffusion ; dans lequel :
    dans le substrat R1 mFenBpM2 w, le R1 est choisi parmi un, deux ou plus des éléments suivants : Pr, Nd, Dy, Tb, Ho, Gd, Ce, La et Y ; Fe représente l'élément fer ; B représente l'élément bore ; M2 est choisi parmi un, deux ou plus des éléments suivants : Ti, Zr, Co, V, Nb, Ni, Cu, Al et Ga ; m représente la teneur de R1 en pourcentage en poids, et 35 % ≥ m ≥ 27 % ; n représente la teneur de Fe en pourcentage en poids, et 70 % ≥ n ≥ 60 % ; p représente la teneur en B en pourcentage en poids, et la teneur de l'élément B est 0,8 % ≤ p ≤ 1,5 % ; et w représente la teneur de M2 en pourcentage en poids, et w = 100%-m-n-p ; et
    l'alliage RH xM1 yBz est tel que défini dans la revendication 1 ou 2.
  8. Procédé selon la revendication 7, dans lequel le R1 est choisi parmi Nd et Dy, et le M2 est choisi parmi Ti, Cu, Ga et Co ;
    de préférence, un procédé de préparation du substrat R1 mFenBpM2 w comprend la fusion, le broyage, le pressage, le frittage et le vieillissement pour préparer un aimant, et peut en outre comprendre les étapes de traitement mécanique et de traitement de surface ;
    de préférence, l'épaisseur du substrat dans une direction d'orientation ne dépasse pas 30 mm ; par exemple, l'épaisseur est de 1 à 30 mm.
  9. Procédé selon la revendication 7 ou 8, comprenant les étapes suivantes :
    le mélange uniforme de l'alliage R1 xM1 yBz source de diffusion et du substrat R1 mFenBpM2. et la réalisation d'un traitement thermique par diffusion pour obtenir l'aimant fritté néodyme-fer-bore ;
    de préférence, le rapport massique entre l'alliage RH xM1 yBz source de diffusion et le substrat R1 mFenBpM2 w est (1 à 5):1 ;
    de préférence, le traitement thermique par diffusion est réalisé en utilisant un mode de chauffage et
    de refroidissement par paliers ; de préférence, un mode de chauffage et de refroidissement en trois paliers est utilisé ;
    de préférence, dans le premier palier du mode de chauffage et de refroidissement en trois paliers, la température est élevée jusqu'à 300 à 650 °C et maintenue pendant 1 à 8 h ;
    dans le deuxième palier, la température est élevée jusqu'à 750 à 980 °C et maintenue pendant 7 à 50 h ;
    dans le troisième palier, la température est abaissée jusqu'à 700 à 930 °C et maintenue pendant 3 à 20 h ;
    de préférence, pour les différents paliers, la vitesse de chauffage est de 3 à 15 °C/min et la vitesse de refroidissement est de 5 à 30 °C/min ;
    de préférence, le traitement thermique par diffusion comprend en outre un traitement de vieillissement ;
    de préférence, le traitement de vieillissement est réalisé à une température de 400 à 680 °C, et le traitement de vieillissement est réalisé avec un temps de maintien de température de 2 à 10 h.
EP22845354.4A 2021-07-20 2022-07-20 Aimant en néodyme-fer-bore fritté haute performance et son procédé de préparation Active EP4358103B1 (fr)

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CN119601332B (zh) * 2024-11-27 2025-12-26 江西理工大学 一种多合金高综合性能磁体及其制备方法
CN121709361A (zh) * 2026-02-13 2026-03-20 中国科学院宁波材料技术与工程研究所 一种高性能稀土钕基再生磁体及其制备方法与应用

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